Phenylhydrazone derivatives

ABSTRACT

1. A PHENYLHYDRAZONE DERIVATIVE OF THE FORMULA:   1-R2,2-R3,4-(R-C(-CL)=N-NH-),5-R1-BENZENE   WHEREIN R REPRESENTS ALKYL OF 1 THROUGH 4 CARBON ATOMS, AND TWO OF THE SYMBOLS R1, R2 AND R3 REPRESENTS HALOGEN AND THE THIRD REPRESENTS HALOGEN OR NITRO.

United States Patent Office Patented Nov. 12, 1974 3,847,987 PHENYLHYDRAZONE DERIVATIVES Roger Boesch, Vitry-sur-Seine, France, assignor to Rhone-Poulenc S.A., Paris, France No Drawing. Filed May 24, 1973, Ser. No. 363,651 Claims priority, application France, May 26, 1972, 7218895; Mar. 19, 1973, 7309754 Int. Cl. C07c 109/14 US. Cl. 260-506 B Claims ABSTRACT OF THE DISCLOSURE Phenylhydrazone derivatives of the formula:

wherein R represents alkyl containing 1 to 4 carbon atoms, and two of the symbols R R and R represent a halogen atom and the third represents a halogen atom or a nitro radical, are new compounds possessing insecticidal and acaricidal properties.

This invention relates to new phenylhydrazone derivatives, to a process for their preparation and to compositions containing them.

The phenylhydrazone derivatives of the present invention are those of the general formula:

wherein R represents a straightor branched-chain alkyl radical containing 1 to 4 carbon atoms, and two of the symbols R R and R represent a halogen (preferably chlorine) atom and the third symbol represents a halogen (preferably chlorine) atom or a nitro radical.

According to a feature of the present invention, the phenylhydrazone derivatives of general formula I are prepared by the action of a chlorinating agent, such as phosphorus pentachloride, phosphorus oxychloride or thionyl chloride, on a phenylhydrazide of the general formula:

wherein R, R R and R are as hereinbefore defined.

Preferably phosphorus pentachloride is used as the chlorinating agent and the reaction can then be represented schematically in the following manner:

R-Qn-rho-R 21101 P0012 c1 R wherein the 'various R symbols are as hereinbefore defined, and Ar represents a phenyl radical which is optionally substituted, for example, by an alkyl radical.

Conversion of the grouping NHCOR in the phenylhydrazides of general formula K into a grouping is generally effected by heating the phenylhydrazide of general formula II and phosphorus pentachloride in an inert organic solvent such as carbon tetrachloride, preferably at the reflux temperature of the solvent employed, e.g. about C. Decomposition of the phosphorylated complex obtained can be effected by heating with a phe no] in the same inert organic solvent.

When thionyl chloride is employed as the chlorinating agent the reaction can be represented schematically as follows:

(wherein R is as hereinbefore defined) on a nitrobenzene of the general formula:

l rag-Q01 N0: IV

wherein R and R represent halogen atoms.

The phenylhydrazides of general formula H, wherein R and R each represent a halogen atom and R represents a halogen atom or a nitro radical, can be obtained by the action of an acid of the general formula:

R-COOH V (wherein R is as hereinbefore defined), or a derivative 3 of the acid, s'uch as a halide or the anhydride, ylhydrazine of the general formula:

R1 VI wherein R R and R are as hereinbefore defined. The reaction is generally carried out in an inert organic solvent such as methylene chloride, ethyl acetate or an aromatic hydrocarbon such as benzene.

The phenylhydrazines of general formula VI can be obtained by diazotization of the corresponding anilines and reduction of the resulting diazonium salts.

The phenylhydrazone derivatives of general formula I obtained by the afore-described process can optionally be purified by application of physical methods such as crys tallisation or chromatography.

The new compounds of general formula I possess interesting insecticidal and acaricidal properties.

The insecticidal activity is manifest more particularly against diptera (Musca domestica), coleoptera (Tribolium confusum) and lepidoptem (Plutella m'aculipemlis caterpillars) at amounts between I and 100 grams of active material per hectolitre of liquid diluent. The acaricidal activity is interesting against phytophagous acarids (Tetranychas telarz'us) at amounts between 1 and 100 grams of active substance per hectolitre of liquid diluent. At amounts between and 200 grams of active material per hectolitre of liquid diluent the phenylhydrazone derivatives of general formula I show a considerable ovicidal activity.

Compounds of general formula I of outstanding importance are those in which R and R represent chlorine atoms, or one of R and R represents a chlorine atom and the other symbol represents a nitro radical, and R represents a chlorine atom, for example 1-(4,5-dichloro- 2 nitrophenyl-hydrazono)-1-chloro-2,2-dimethylpropane, 1-(2,4-dichloro-5-nitrophenyl-hydrazono) 1 chloro-2,2- dimethylpropane, 1 (2,4,5-trichlorophenyl-hydrazono)-lchloropropane, l-(2,4,5-trichlorophenyl hydrazono)-lchloro 2,2 dimethylpropane, l-(2,4,5-trichlorophenylhydrazono)-l-cbloroethane, 1 (2,4,5 trichlorophenylhydrazono)-l-chlorobutane and 1.-(2,4,5-trichlorophenylhydrazono)-l-chloro-Z-methylpropane.

According to a further feature of thepresent invention, there are provided insecticidal and acaricidal compositions which contain, as the active ingredient, at least one of the phenylhydrazone derivatives of general formula I in association with one or more diluents or adjuvants com patible with the phenylhydrazone derivative(s) and suitable for use in agriculture.

These compositions can optionally contain other compatible pesticides such as fungicides (e.g. maneb). Preferably the compositions contain between 0.005% and 80% by weight of phenylhydrazone derivatives.

The compositions may be solid if there is employed a powdered solid compatible diluent such as talc, calcined magnesia, kieselguhr, tricalcium phosphate, powdered cork, adsorbent charcoal, or a clay such as kaolin or bentonite. These solid compositions are preferably prepared by grinding the phenylhydrazone derivative with the solid diluent, or by impregnating the solid diluent with a solution of the phenylhydrazone derivative in a volatile solvent, evaporating the solvent, and it necessary grinding the product so as to obtain a powder.

Instead'of a solid diluent, there may be used a liquid in which the phenylhydrazone derivative is dissolved or dispersed. The compositions may thus take the form of suspensions, emulsions or solutions in organic or aqueousorganic media, for example aromatic hydrocarbons such as toluene or xylene, mineral, animal or vegetable oils, or acetophenone, or mixtures of these diluents. Thecomon a phenpositions in the form of suspensions, emulsions or solutions may contain wetting, dispersing or emulsifying agents of the ionic or non-ionic type, for example sulphoricinoleates, quaternary ammonium derivatives or products based on condensates of ethylene oxide such as the condensates of ethylene oxide with octylphenol, or fatty acid esters of anhydrosorbitols which have been rendered soluble by etherification of the free hydroxyl groups by condensation with ethylene oxide. It is preferable to use agents of the non-ionic type because they are not sensitive to electrolytes. When emulsions are required the phenylhydrazone derivatives may be used in the form of self-emulsifying concentrates containing the active substance dissolved in the emulsifying agent or in a solvent containing an emulsifying agent compatible with the phenylhydrazone derivative and solvent, a simple addition of water to such concentrates producing compositions read for use.

The phenylhydrazone derivatives of general formula I are preferably employed for insecticidal and acaricidal purposes in quantities of 10 to g. per hectolitre of water, but lower concentrations can also be used effectively.

The following Example illustrates the preparation of phenylhydrazone derivatives of general formula I.

EXAMPLE 1 A suspension of l-(4,S-dichloro-Z-nitrophenyl)-2- trimethylacetyl-hydrazine (739 g.) and phosphorus pentachloride (517 g.) in carbon tetrachloride (4.8 litres) is heated until the evolution of gas ceases, the reaction mixture being taken progressively to the reflux temperature. To the solution obtained there is added, after cooling to 20 C., a solution of phenol in carbon tetrachloride (3.36 litres) containing 2.36 moles of phenol per litre. The reaction mixture is then heated at the reflux temperature until the evolution of gas finishes. It is then cooled to 20 C., filtered and the resulting solution is concentrated under reduced pressure (20 mm. Hg.) at 60 C. The residue is purified by chromatography on Kieselgel, elution being effected with a mixture of heptane and diethyl ether (9.5 0.5 by volume). After recrystallisation from isopropanol and then heptane, there is obtained l-(4,5-dichloro-2-nitrophenyl hydrazono)-l-chloro-2,2-dimethylpropane (498 g.) melting at 99-100 C.

The l-(4,5 dichloro-Z-nitrophenyl)-2-trimethylacetylhydrazine, m-.p. 153 C., employed as starting material can be obtained by the action of trimethylacetylhydrazine on 2,4,S-trichloronitrobenzene in N-methylpyrrolid-Z-one.

By proceeding as described in the foregoing Example and starting with appropriate phenylhydrazides of general formula II, there are prepared the following phenylhydrazone derivatives conforming to general formula I:

1- 2,4-dichloro-5-nitrophenyl-hydr azono -1-chloro-2,2-

dimethylpropane, mLp. 109 C.;

1- 2,4,5-trichlorophenyl-hydrazono l-chloropropane,

solidification point 40 C.;

l- 2,4, 5-trichlorophenyl-hydrazono)-1-chloro-2,2di-

methylpropane, m.p. 76 C.;

l-(2,4,5-trichlorophenyl-hydrazono) -1-chloroethane, m.p.

1- (2,4, 5-trichlorophenyl-hydrazono l-chlorobutane,

solidification point 34 C., and

1- 2,4, 5-trichlorophenyl-hydrazono -1-chloro-2 methylpropane, m.p. 57 C.

The following Examples illustrate compositions according to the invention.

EXAMPLE 2 5 g. of a condensation product of octylphenol and ethylene oxide containing 10 molecules of ethylene oxide per molecule of octylphenol are added to 20 g. of l-(4,5-dichloro-2-nitrophenyl-hydrazono)-l-chloro 2,2 dimethylpropane, and a mixture of equal volumes of toluene and acetophenone are added until the mixture reaches 100 cc.

The solution thus obtained is utilised after suitable dilution with water to destroy acarids. According to the eifect required, concentrations of to 100 g. of phenylhydrazone derivative per hectolitre of water give good results.

EXAMPLE 3 To 50 parts of 1-(4,5-dichloro-2-nitrophenyl hydrozono)-1-chloro-2,Z-dimethylpropane there are added 1 part of Tween 80 (the mono-oleate of a polyoxyethylene derivative of sorbitol), parts of calcium lignosulphite and 29 parts of kieselguhr. After grinding and sieving, the powder obtained is utilised after dilution with water to destroy acarids.

The parts referred to above are parts by weight.

I claim:

1. A phenylhydrazone derivative of the formula:

5. The phenylhydrazone derivative according to claim 1 which is 1-(2,4-dichloro-5 nitrophenyl hydrazono)-lchloro-2,2-dimethylpropane.

6. The phenylhydrazone derivative according to claim 1 which is 1-(2,4,5-trichlorophenyl hydrazono)-1-chloropropane.

7. The phenylhydrazone derivative according to claim 1 which is l-(2,4,5-trichlorophenyl hydrazono)-1-chloro- 2,2-dimethylpropane.

8. The phenylhydrazone derivative according to claim 1 which is 1-(2,4,5-trichlorophenyl hydrazono)-1-chloroethane.

9. The phenylhydrazone derivative according to claim 1 which is 1-(2,4,5-trich1orophenyl hydrazono)-1- chlorobutane.

10. The phenylhydrazone derivative according to claim 1 which is 1-(2,4,5-trich1orophenyl-hydrazono)-1-ch1oro- Z-methylpropane.

References Cited UNITED STATES PATENTS 1/1972 Draber et a1 260566 B OTHER REFERENCES Chemical Abstracts, vol. 49, column 13140(d).

BERNARD HEL'FIN, Primary Examiner G. A. SCHWARTZ, Assistant Examiner U.S. Cl. X.R. 260543 P; 424-327 Notice of Adverse Decision in Interference In Interference No. 99,552, involving Patent No. 3,847,987, R. Boesch, PHENYLHYDRAZON E DERIVATIVES, final judgment adverse to the patentee was rendered Sept. 19, 1977, as to claims 1, 2 and 410.

[Ofieial Gazette December 20, 1977.] 

1. A PHENYLHYDRAZONE DERIVATIVE OF THE FORMULA: 